Light emitting device with phase changing off state white material and methods of manufacture

ABSTRACT

Light emitting devices (LEDs) are described herein. An LED includes a light emitting semiconductor structure, a wavelength converting material and an off state white material. The light emitting semiconductor structure includes a light-emitting active layer disposed between an n-layer and a p-layer. The wavelength converting material has a first surface adjacent the light emitting semiconductor structure and a second surface opposite the first surface. The off state white material is in direct contact with the second surface of the wavelength converting material and includes multiple core-shell particles disposed in an optically functional material. Each of the core-shell particles includes a core material encased in a polymer or inorganic shell. The core material includes a phase change material.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/722,903, filed Oct. 2, 2017, which claims the benefit of U.S.Provisional Patent Application No. 62/403,994 filed Oct. 4, 2016, whichis incorporated by reference as if fully set forth herein.

BACKGROUND

Light emitting diodes may be used as white light sources in variousapplications, such as flash sources for cellular telephone cameras andfilament lamps. Such LEDs may be referred to herein as white LEDs. WhiteLEDs may appear to emit white light from the perspective of the viewerwhen the LEDs are in an on state. However, they may actually be made upof light emitting semiconductor structures that emit non-white light aswell as wavelength converting structures that make the non-white lightappear white to the viewer. For example, a white LED may be formed froma blue light emitting semiconductor structure covered by a yellowemitting phosphor layer. Photons of blue light emitted by the lightemitting semiconductor structure may either pass through the yellowemitting phosphor layer as blue photons or may be converted into yellowphotons by the yellow emitting phosphor layer. The blue and yellowphotons that are ultimately emitted out of the LED combine to make thelight emitted from the LED appear white to the viewer.

SUMMARY

Light emitting devices (LEDs) are described herein. An LED includes alight emitting semiconductor structure, a wavelength converting materialand an off state white material. The light emitting semiconductorstructure includes a light-emitting active layer disposed between ann-layer and a p-layer. The wavelength converting material has a firstsurface adjacent the light emitting semiconductor structure and a secondsurface opposite the first surface. The off state white material is indirect contact with the second surface of the wavelength convertingmaterial and includes multiple core-shell particles disposed in anoptically functional material. Each of the core-shell particles includesa core material encased in a polymer or inorganic shell. The corematerial includes a phase change material.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a diagram of an example light emitting device (LED) thatincludes a light emitting semiconductor structure and an off state whitematerial;

FIG. 1B is a diagram of an example light emitting semiconductorstructure that may be included in the LED of FIG. 1A;

FIG. 1C is a diagram of an example layer of an off state white materialthat may be included in the LED of FIG. 1A;

FIG. 2A is a diagram of an example flash LED including an off statewhite material;

FIG. 2B is a diagram of another example flash LED including an off statewhite material; and

FIG. 3 is a flow diagram of a method of manufacturing an LED with an offstate white material.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

While white LEDs may appear to emit white light in their on states, suchLEDs may appear to be the color of the wavelength converting materialwhen turned off. For example, a white LED that includes a yellowemitting phosphor layer may appear yellow or green to a viewer whenturned off, such as when being viewed on a store shelf. Nevertheless, anordinary consumer may expect a product that includes a white LED toappear white even in the off state. For example, a person who walks intoa store to purchase a white light bulb will usually expect the whitelight bulb to actually appear white and may think that the light bulb isdefective if it appears yellow or green. The same may be true of acellular telephone consumer who may expect the camera flash to appearwhite. Such products would be more marketable to the consumer if the LEDappeared white in the off state as well as in the on state.

Granules of white, non-phosphor, inert materials have been used toprovide an off-state white appearance for LEDs. Examples of suchmaterials include Titanium Dioxide (TiOx) and Zirconium Oxide (ZrOx).Sub-micron size particles of these materials may be mixed in with atransparent material, such as silicone, and applied over a non-white LEDsurface to make it appear whiter to a viewer in the LED off state.However, such granules of white, non-phosphor, inert materials remainwhite while the device is on. Thus, they may provide some scattering oflight emitted from the LED, reducing the LED's lumen output.

Embodiments described herein provide for a white LED that may appearwhite to the viewer in both the LED on and off states, and also reduceor eliminate scattering in the LED on state, making products thatinclude such LEDs more aesthetically pleasing to the viewer withoutimpacting the quality of the LED itself. Such embodiments may make useof phase change materials (PCMs), such as paraffin waxes and deuteratedparaffin analogs, applied over a non-white LED surface. Such PCMs mayappear white at room temperature when the LED is in the off state butmay change phase and become transparent or more transparent when heatedas a result of the LED being turned on. Further, for a PCM and anon-PCM, such as ZiOx or ZrOx, having equal whiteness in the off state,losses in the on state may be lower for the PCM than other off statewhite materials because scattering is decreased for the PCMs atoperating temperature. If the same losses are accepted, a whiter layermay be made with the PCMs.

FIG. 1A is a diagram of an example light emitting device (LED) 100 thatincludes a light emitting semiconductor structure 115, a wavelengthconverting material 110, and an off state white material 105. Contacts120 and 125 may be coupled to the light emitting semiconductor structure115, either directly or via another structure such as a submount, forelectrical connection to a circuit board or other substrate or device.In embodiments, the contacts 120 and 125 may be electrically insulatedfrom one another by a gap 127, which may be filled with a dielectricmaterial. The contacts or interconnects 120 and 125 may be, for example,solder, stud bumps, or gold layers.

The light emitting semiconductor structure 115 may be any light emittingsemiconductor structure that emits light that may be converted to whitelight via a wavelength conversion material. An example of such a lightemitting semiconductor structure 115 is a III-nitride light emittingsemiconductor structure that emits blue or UV light, such as a lightemitting semiconductor structure formed from one or more of binary,ternary, and quaternary alloys of gallium, aluminum, indium, andnitrogen. Other examples of light emitting semiconductor structures mayinclude light emitting semiconductor structures formed from group III-Vmaterials, II-phosphide materials, III-arsenide materials, II-VImaterials, zinc oxide (ZnO), or Silicon (Si)-based materials.

FIG. 1B is a diagram of an example light emitting semiconductorstructure 115 that may be included in the LED 100 of FIG. 1A. Theillustrated example is a flip chip structure. However, one of ordinaryskill in the art will understand that the embodiments described hereinmay be applied to other types of LED designs, such as vertical, lateral,and multi-junction devices.

In the example illustrated in FIG. 1B, the light emitting semiconductorstructure 115 includes a light emitting active region 135 disposedbetween an n-type region 130 and a p-type region 140. Contacts 145 and150 are disposed in contact with a surface of the light emittingsemiconductor structure 115 and electrically insulated from one anotherby a gap 155, which may be filled by a dielectric material, such as anoxide of silicon. In the illustrated embodiment, contact 145 (alsoreferred to as a p-contact) is in direct contact with a surface of thep-type region 140 and the contact 150 (also referred to as an n-contact)is in direct contact with a surface of the n-type region 130.

The n-type region 130 may be grown on a growth substrate and may includeone or more layers of semiconductor material. Such layer or layers mayinclude different compositions and dopant concentrations including, forexample, preparation layers, such as buffer or nucleation layers, and/orlayers designed to facilitate removal of the growth substrate. Theselayers may be n-type or not intentionally doped, or may even be p-typedevice layers. The layers may be designed for particular optical,material, or electrical properties desirable for the light emittingregion to efficiently emit light. Like the n-type region 130, the p-typeregion 140 may include multiple layers of different composition,thickness, and dopant concentrations, including layers that are notintentionally doped, or n-type layers. While layer 130 is describedherein as the n-type region and layer 140 is described herein as thep-type region, the n-type and p-type regions could also be switchedwithout departing from the scope of the embodiments described herein.

The light emitting active region 135 may include a single thick or thinlight emitting layer. Alternatively, the light emitting active region135 may be a multiple quantum well light emitting region, which mayinclude multiple thin or thick light emitting layers separated bybarrier layers.

The p-contact 145 may be formed on a surface of the p-type region 140.The p-contact 145 may include multiple conductive layers, such as areflective metal and a guard metal, which may prevent or reduceelectromigration of the reflective metal. The reflective metal may besilver or any other suitable material. The re-contact 150 may be formedin contact with a surface of the n-type region 130 in a region whereportions of the active region 135, the n-type region 140, and thep-contact 145 have been removed to expose at least a portion of thesurface of the n-type region 130.

The n-contact 150 and p-contact 145 are not limited to the arrangementillustrated in FIG. 1B and may be arranged in any number of differentways. In embodiments, one or more n-contact vias may be formed in thelight emitting semiconductor structure 115 to make electrical contactbetween the re-contact 150 and the n-type layer 130. Alternatively, then-contact 150 and p-contact 145 may be redistributed to form bond padswith a dielectric/metal stack as known in the art. The p-contact 145 andthe n-contact 150 may be electrically connected to the contacts 120 and125 of FIG. 1A, respectively, either directly or via another structure,such as a submount.

The wavelength conversion material 110 may be any luminescent material,such as a phosphor or phosphor particles in a transparent or translucentbinder or matrix that absorbs light of one wavelength and emits light ofa different wavelength. The wavelength conversion material 110 may beapplied in a layer having a thickness that may depend on the wavelengthconversion material used. For example, a layer of wavelength conversionmaterial 110 may be approximately 50 μm in thickness while otherwavelength conversion materials may be formed in layers as thin as 20 μmor as thick as 100 μm. In embodiments, the wavelength conversionmaterial 110 may be pre-formed into a wavelength conversion element andattached to the light emitting semiconductor structure 115 using anadhesive or any other method or material known in the art.

In embodiments, the light emitting semiconductor structure 115 emitsblue light. In such embodiments, the wavelength conversion material 110may include, for example, a yellow emitting wavelength conversionmaterial or green and red emitting wavelength conversion materials,which will produce white light when the light emitted by the respectivephosphors combines with the blue light emitted by the light emittingsemiconductor structure 115. In other embodiments, the light emittingsemiconductor structure 115 emits UV light. In such embodiments, thewavelength conversion material 110 may include, for example, blue andyellow wavelength converting materials or blue, green and red wavelengthconverting materials. Wavelength converting materials emitting othercolors of light may be added to tailor the spectrum of light emittedfrom the device 100.

The wavelength converting material 110 may include conventional phosphorparticles, organic semiconductors, II-VI or III-V semiconductors, II-VIor III-V quantum dots or nanocrystals, dyes, polymers, or materials suchas gallium nitride (GaN) that luminesce. Any suitable phosphor may beused, including garnet-based phosphors, such as Y₃Al₅O₁₂:Ce (YAG),Lu₃Al₅O₁₂:Ce (LuAG), Y₃Al_(5-x)Ga_(x)O₁₂:Ce (YAlGaG),(Ba_(1-x)Sr_(x)),SiO₃:Eu (BOSE), and nitride-based phosphors, such as(Ca,Sr)AlSiN₃: Eu and (Ca,Sr,Ba)₂Si₅N₈:Eu. In embodiments where thewavelength conversion material is a YAG phosphor, the color temperatureof the white light may depend largely on the Ce doping in the phosphoras well as on the thickness of the phosphor layer.

FIG. 1C is a diagram of an example layer of off state white material 105that may be included in the LED 100 of FIG. 1A. The off state whitematerial 105 may be formed from a plurality of core-shell particles 160disposed in an optically functional material 165, which may be, forexample, silicone or any transparent or near transparent material, or atemperature and light resistant matrix, such as a silicone matrix.

In embodiments described herein, various paraffin waxes, such asdocosane, tricosane, hexacosane, or octacosane, may be used in the offstate white material 105, and the paraffin waxes may be included in thecore material of the core-shell particles 160, as is described in moredetail below. These paraffin materials may appear white at roomtemperature (i.e., when the LED is in the off state). Unlike other whitepigments, such as TiOx, that remain white when the LED is in the onstate, paraffin melts and becomes transparent or near transparent as aresult of the LED being switched on. As a specific example, the heatfrom the LED in the on state causes tricosane, which has a melting pointof 46° C., to melt and become significantly more transparent and,therefore, reduces the amount of scattering of light emitted from thelight emitting semiconductor structure and wavelength conversionmaterial as compared to non-PCMs, such as TiOx. The reduction inscattering achieved using paraffin in the off state white material 105means the light interacts less with surfaces that can absorb the emittedlight and, therefore, the use of a paraffin as the PCM in the off statewhite material 105 results in increased efficiency compared to TiO_(x)in the off state white material.

The specific paraffin to be used may be chosen and adapted based onvarious factors described in more detail below. The chosen paraffinshould, in any event, become transparent, or nearly transparent, at adevice temperature corresponding to an on state of the LED so that lightemitted by the light emitting semiconductor structure 115 may passthrough with little or no reduction in lumen output as compared to anLED that does not include an off state white material 105.

The improvement gained in reduction of light scattering by using a PCMinstead of white pigments such TiOx in the off state white material maybe negated by degradation of the material, which may cause a decrease inreflectivity and reduce the efficacy when the LED is on, and may alsodecrease the whiteness when the LED is off. For example, experimentationwith use of phase change materials (PCMs) has presented a problem thatboth the processing and operational conditions of LEDs (e.g., highsoldering temperatures) cause degradation of the paraffin wax, which maydrastically affect lumen output of the LED. For example, operation at350 mA and 80° C. does not lead to degradation of a TiO_(x) containingoff state white material, but the LED performance of an LED with aparaffin-containing off state white material decreases after tens tohundreds of hours.

Further, as paraffin waxes are organic materials, and LEDs operate athigh light flux and temperature, thermal and photo-thermal degradationmay be a concern for the use of these PCMs for LED applications. Morespecifically, it has been observed that PCMs may degrade and reduce inswitching amplitude between white and transparent or nearly transparentafter repeated switching and may even turn yellow or brown over time.This may result from light or heat induced chemical modifications,changing the crystallization of the paraffin and leading to slowerswitching amplitude. The breaking of a carbon-hydrogen (C—H) bond in theparaffin may be the starting point for changes that may ultimately leadto ceasing of the switching behavior of the paraffin. The reduction ofthe switching behavior has been observed to be less for an encapsulatedparaffin in silicone, but to an insufficient extent, indicating theimportance of the breakage of C-H bonds as a first step in thedegradation of the of the paraffin material.

The observed degradation for paraffin materials over time may besubstantially mitigated or eliminated by replacing the C—H bonds withcarbon-deuterium (C-D) bonds to create a deuterated paraffin analog. Byusing a deuterated paraffin analog as opposed to a non-deuteratedparaffin in the off state white material 115, a C-D bond would have tobreak to start the degradation process. However, the C-D bond isstronger than the C—H bond due to the kinetic isotope effect and, thus,the deuterated paraffin may be more stable for use on an LED. Morespecifically, at room temperature, the reaction rate for breaking theC-D versus the C—H bond is a factor 7 such that the difference inreaction rates between a paraffin and a deuterated paraffin analog mayamount up to 7 times.

Depending on the desired switching temperature of the deuteratedparaffin analog, different chain lengths may be chosen. For example, adeuterated paraffin may be chosen that has a high enough melting pointsuch that it does not melt at ambient or close to body temperature and alow enough melting point that it melts when the LED is switched on. Inembodiments, a deuterated paraffin with a melting point at or lower than40° C. may be used. For most applications, a deuterated paraffin with amelting point with a maximum value of less than 100° C. may be chosen.For flash applications, a deuterated paraffin with an even highermelting point may be chosen, such as a deuterated paraffin with amaximum melting point of 150° C. In all applications, the chosenparaffin should have a melting point in the temperature range reachedwhen the LED is switched on at the relevant current and should show acrystalline solid to liquid transition. In the solid state, the chosenparaffin should be sufficiently scattering so as to appear white to aviewer in ambient lighting. Given the melting point considerations forparaffins described above, it should be noted that a paraffin with alower melting point will melt more quickly than a paraffin with a highermelting point and, therefore, will allow for a quicker switching timebetween the on and off states. However, a paraffin with a higher meltingpoint, while slower to switch between the on and off states, will have aslower evaporation rate and, therefore, use of a such a paraffin as thePCM in an off state white material may result in slower evaporation andhelp to reduce degradation by loss of paraffin over time.

In embodiments, deuterated tricosane may be used. Other exampledeuterated paraffin analogs that may be suitable for use in an LEDdepending on desired switching temperature may include deuterateddocosane (C₂₂D₄₆), which has a switching temperature of 43° C.,deuterated hexacosane, which has a switching temperature of 56° C., anddeuterated octacosane, which has a switching temperature of 64° C.

Paraffin waxes and deuterated paraffin analogs may be particularlyuseful as off state white materials because they begin to melt at aparticular melting temperature, resulting in the paraffin changing fromwhite to transparent or near transparent. However, due to the phasechange of the materials (i.e., melting) that causes the change intransparency of the material, a mechanism is needed to contain theparaffin so that it does not diffuse out of the device (or layer 105).The optically functional material 165, such as silicone, cannot, itself,prevent the paraffin or deuterated paraffin analog from diffusing out.

In embodiments, the paraffin or deuterated paraffin analog may beencapsulated in core-shell particles 160. In embodiments, the paraffinor deuterated paraffin analog may be encapsulated in the core-shellparticles 160 along with a nucleation agent (e.g., stearic acid) for theliquid-solid transition that may be present at concentrations of 1% orapproximately 1%. The core-shell particles 160 may be dispersed orembedded in an optically functional material 165 to form the off statewhite material 105.

The optically functional material 165 may be a polymer, such assilicone, a temperature and light resistant matrix, such as an opticalgrade silicone matrix, or any other suitable material, such as a sol-gelmaterial, an organically modified ceramic (ormocer), or a polysilizanebased matrix. The shells for the particles may be polymer or inorganicshells, such as melamine formaldehyde-based shells or silica-basedshells. The core-shell particles may have a diameter in the range of 1μm to 50 μm. In embodiments, the core-shell particles may have adiameter in the range of 1 μm to 20 μm.

An acceptable range of thicknesses for the shells may depend on therefractive index of the shell. If the refractive index of the shell isthe same as or close to the refractive index of the paraffin orsilicone, shell thickness may not matter. If the refractive index of theshell is higher than the paraffin or silicone, the shell may beresponsible for residual scattering. In all cases, the shell should bethick enough to contain the paraffin during handling and layerpreparation and to subsequently maintain the paraffin encased within theshell during operation of the device.

In FIG. 1C, an off state white material 105 is illustrated, includingthe encapsulated particles 160 disposed in the optically functionalmaterial 165. The off state white material 105 may be applied directlyto the phosphor material 110 or other exposed surface of an LED to makethe LED appear whiter to the viewer. As with the deuterating of theparaffin, the LED may be further improved to have an even greaterphoto-thermal stability by deuterating other organic components of theLED, such as the nucleation agent or the polymer shell.

In embodiments, the off state white material 105 may be formed into alayer or film having a thickness, t. The thickness, t, may be chosen tooptimize the switching speed of the phase changing material, thephysical space taken up by the off state white material 105 in the lightemitting semiconductor structure 115, and the overall whiteness of theoff state white material 105. For example, a thicker layer may heat upmore slowly and, therefore, may cause the phase change material toswitch more slowly. A thicker layer may also take up more physical spacein the light emitting semiconductor structure 115. However, there is alimit to the volume fraction of phase change material containing coreshell particles that can be incorporated into an optically functionalmaterial and, therefore, if the off state white material 105 is formedinto a layer that is too thin, the material may not achieve optimalwhiteness in the off state. In embodiments, a layer of the off statewhite material 105 may have a thickness, t, of 50 μm. However, the layermay have a thickness, t, as thick as, for example, 100 μm or 200 μm.

To be able to work with a thin layer of off state white material 105,such as the example 50 μm thick layer described above, a high volumefraction of encapsulated paraffin may be used to make the layer appearas white as possible in the LED off state. The upper limit of the volumefraction may be determined by the maximum packing of the paraffincapsules. If this number is exceeded, the layer will contain pores orbecome very rough. The upper limit depends on the size distribution ofthe specific sample. For example, in an ordered array, the most densepacking of equal sized spheres would be 74%, and with random packing,would be 64%. In embodiments, the volume fraction of encapsulatedparaffin in the off state white material 105 may be in the range of5%-40% or 50%. Within these ranges, a volume fraction of 20% may beconsidered to be easily attainable and 50% may be considered to be veryhigh and not possible for every sample.

The shells of the core-shell particles 160 may be subject to certainstresses as a result of the repeated phase change of the PCMs from solidto liquid as the LEDs switch between their off and on states. It hasbeen observed that oxidation of the polymer shell due light andtemperature exposure combined with the repeated expansion andcontraction may lead to embrittlement of the shell and may eventuallycause cracking during a phase change event. The cracked shell may nolonger be able to confine the PCM, leading to core material loss due toevaporation. In embodiments, an amount of material that does not undergoa phase change may be introduced into the core with the paraffin ordeuterated paraffin analog material to reduce stress on the shell,prolong the life of the materials, and improve LED reliability. Inembodiments, a material may be chosen that has properties similar to theoptically functional material in light and heat stability. Examples ofsuitable materials may include a silicone polymer, polysilizanes,sol-gel materials and organically modified ceramics (ormocers). Inembodiments, a ratio of 50% to 90% silicone to paraffin or deuteratedparaffin analog may be introduced into the core to minimize stress onthe shell due to phase changes while maintaining the desirable off statewhite properties of the off state white material.

It should also be noted that the magnitude of the PCM for opticalswitching may be determined by the grain size of each PCM domain. For asingle domain of paraffin in a polymer shell, there would be minimaloptical scattering. Increasing the number of randomly oriented domainsof paraffin in a single shell may increase the scattering power of eachcapsule in the off state. The use of silicone polymer as a filler in thecapsules may aid in generating more domains and, therefore, increase thescattering power per amount of paraffin. This may be desirable in theoff state to create a more white appearance to the LED.

It should also be noted that, while advantages of the off state whitematerial are described herein for use to cover up the non-whiteappearance of a wavelength converting layer, the off state whitematerial 105 may be equally applicable for use on a surface of an LEDother than on a wavelength converting layer 110 where it is desirable tomake the surface appear more white. The silicone or other opticallyfunctional material on such a surface of an LED may also protect thesemiconductor LED die and further increase light extraction. White LEDswith an off state white material 105 may be used in many different typesof applications. One typical example is a flash LED, and examples areprovided below with respect to FIGS. 2A and 2B.

FIG. 2A is a diagram of an example flash LED 200A including an off statewhite material. In the example illustrated in FIG. 2A, the flash LED200A includes the light emitting semiconductor structure 115 of FIG. 1B,which is mounted to a submount 205 that includes the contacts 120 and125. The light emitting semiconductor structure 115 may be mounted tothe submount 205 by an electrical coupling between the contacts 145 and150 on the light emitting semiconductor structure 115 and submountelectrodes on an adjacent surface of the submount 205 (not shown in FIG.2A). The submount electrodes may be electrically connected by vias (notshown) to the contacts 120 and 125 on the opposite surface of thesubmount 205. The submount 205 may be mounted via the contacts 120 and125 to a printed circuit board (not shown), which may form a part of theflash module for a camera in embodiments. Metal traces on the circuitboard may electrically couple the contacts 120 and 125 to a powersupply, such that an operational voltage and current may be applied tothe LED when it is desired to turn the LED on.

The submount 205 may be formed from any suitable material, such asceramic, Si, or aluminum. If the submount material is conductive, aninsulating material may be disposed over the substrate material, and themetal electrode pattern may be formed over the insulating material. Thesubmount 205 may act as a mechanical support, provide an electricalinterface between the delicate n and p electrodes on the LED chip and apower supply, and provide heat sinking.

In the example flash LED 200A, the wavelength converting material 110completely surrounds the light emitting semiconductor structure 115 onall surfaces except the surface that electrically connects the lightemitting semiconductor structure 115 to the submount 205. The off statewhite material 105 with optically functional material 165 and core-shellparticles 160 is disposed in direct contact with the wavelengthconversion material 110.

FIG. 2B is a diagram 200B of another example flash LED 200B including anoff state white material. In the example flash LED 200B, the wavelengthconverting material 110 is deposited on the light emitting semiconductorstructure 115. The off state white material 105 with opticallyfunctional material 165 and core-shell particles 160 is disposed indirect contact with the wavelength conversion material 110. A structure210, such as a frame, is disposed adjacent side surfaces of a stackformed by the light emitting semiconductor structure 115, the wavelengthconverting material 110 and the off state white material 105 and maysurround the stack. The entire structure 210, but at least innersurfaces of the structure 210 that are adjacent the stack, may be formedfrom or coated in a light reflecting material, such as an interferencelayer or a strongly scattering layer, to further minimize absorption ofany scattered light.

FIG. 3 is a flow diagram 300 of a method of manufacturing an LED with anoff state white material. The example method 300 includes creating thelight emitting semiconductor structure 115 (305). The light emittingsemiconductor structure may be created, for example, by growing thelight emitting semiconductor structure, such as a III-nitridesemiconductor structure, on a growth substrate. The growth substrate maybe, for example, sapphire or any other suitable substrate such as anSiC, Si, GaN or a composite substrate. In embodiments, the n-type region130 may be grown first. The light emitting active region 135 may begrown over the n-type region 130. The p-type region 140 may be grownover the light emitting active region 135. After growth, the p-contact145 may be formed on a surface of the p-type region 140, and then aportion of the p-contact 145, a portion of the p-type region 140 and aportion of the light emitting active region 135 may be removed to exposeat least a portion of a surface of the n-type region 130 in contact withwhich the n-contact 150 may be formed.

In embodiments, such as where the LED 100 is used in an LED flash, suchas illustrated in FIG. 2A or 2B, the light emitting semiconductorstructure 115 may be mounted on a submount (e.g., the submount 205 inFIG. 2A or 2B) as a flip chip. The surface of the submount adjacent then-contact 150 and the p-contact 145 may include metal electrodes thatmay be soldered or ultrasonically welded to the contacts 145 and 150,for example, via solder balls Other types of bonding may also be used.The solders balls may be omitted if the electrodes themselves may beultrasonically welded together.

The submount electrodes (not shown in FIGS. 2A and 2B) may beelectrically connected by vias to contacts 120 and 125 (in this example,they are located on a surface of the submount 205 opposite the surfaceof the submount that is adjacent to the contacts 145 and 150) so thesubmount 205 may be surface mounted to metal pads on a printed circuitboard, for example, which may form part of a flash module for a camera(e.g., as in the embodiments illustrated in FIGS. 2A and 2B).

In embodiments, the growth substrate may be removed, for example tocreate a lower profile LED, which may be desirable for the flash modulefor the camera illustrated in and described with respect to FIGS. 2A and2B. The growth substrate may be removed, for example, using chemicalmechanical polishing (CMP) or laser lift-off, where a laser heats theinterface between the light emitting semiconductor structure 115 and thegrowth substrate to create a high-pressure gas that pushes the growthsubstrate away from the light emitting semiconductor structure 115. Inembodiments, the growth substrate may be removed after an array of LEDsis mounted on a submount wafer and prior to the LED/submounts beingsingulated (e.g., by sawing). In other embodiments, the growth substratemay remain attached to the light emitting semiconductor structure and,as a result, may become part of the LED. In such embodiments, the growthsubstrate may be transparent or near transparent to light. In suchembodiments, a surface of the growth substrate on which the lightemitting semiconductor structure is grown may be patterned, roughened,or textured before growth, which may improve light extraction from theLED. Additionally or alternatively, a surface of the growth substrateopposite the growth surface (i.e., the surface through which a majorityof light is extracted in a flip chip configuration) may be patterned,roughened, or textured before growth, which may improve light extractionfrom the LED.

The example method 300 illustrated in FIG. 3 further includes applyingthe wavelength converting material 110 to the light emittingsemiconductor structure 115 (310). In embodiments, the wavelengthconverting material 110 may be a layer or film that is, for example,spray deposited, spun-on or thin-film deposited (e.g., byelectrophoresis). Alternatively, the wavelength converting material 110may be formed into an element, such as a ceramic plate, and affixed tothe light emitting semiconductor structure 115.

The example method 300 illustrated in FIG. 3 further includes creatingthe off state white material 105 (315) and applying it to the wavelengthconverting material 110 or surface of the light emitting semiconductorstructure 115 if no wavelength converting material is included (320).This may be done using any method known in the art, such as mixingfollowed by an application technique.

In embodiments, the off state white material 105, including theoptically functional material 165 and the core-shell particles 160, islaminated to the light emitting semiconductor structure 115 or thewavelength converting material 110 (if included). In embodiments, it maybe molded directly over the light emitting semiconductor structure 115and/or wavelength converting material 110 (if included). If it isdesired to use the off state white material 105 as a lens, the off statewhite material may be shaped using a mold to create an off state whiteswitchable lens or microlens.

The terms transparent, near transparent, and more transparent are usedherein to describe, for example, the off state white material 105 andthe result of the phase change of a PCM from the off (or solid state ofthe PCM) to the on (or liquid state of the PCM). In this regard, if asolid PCM material, such as a paraffin, melts, it becomes a completelytransparent liquid with 100% transparency. However, when theencapsulated PCM materials, as described herein, are disposed in anoptically functional material, such as a silicone matrix, there will bea level of residual scattering when the PCM material is in itscompletely transparent state. This may result from the refractive indexof liquid paraffin differing from that of the optically functionalmaterial, such as the silicone matrix, and also differing from therefractive index of the shell of the particles containing the paraffin.For example, when samples of paraffin containing capsules are tested ona laser-setup at 450 nm, an increase in direct transmission may be seenof about 50% when the paraffin melts. Apart from direct transmission,there is also diffuse transmission, which is difficult to quantify. Asthe off state white material 105 is desired to be very white (e.g.,strongly scattering) in the off state, the initial direct transmissionof the off state white material 105 may be low, such as 2% transparentor less.

Having described the embodiments in detail, those skilled in the artwill appreciate that, given the present description, modifications maybe made to the embodiments described herein without departing from thespirit of the inventive concept. Therefore, it is not intended that thescope of the invention be limited to the specific embodimentsillustrated and described.

1. (canceled)
 2. A light emitting device comprising: a light emittingsemiconductor structure; a wavelength converting structure arranged inan optical path of light emitted by the light emitting semiconductorstructure; and an off state white structure arranged in an optical pathof light emitted by or transmitted through the wavelength convertingstructure, the off state white structure comprising core-shell particlesdispersed in a transparent material, each of the core shell particlescomprising a core material that includes a phase-change material encasedin a shell.
 3. The light emitting device of claim 2, wherein: thewavelength converting structure comprises a first surface adjacent thelight emitting semiconductor structure and a second surface opposite thefirst surface; and the off state white structure is in direct contactwith the second surface of the wavelength converting structure.
 4. Thelight emitting device of claim 2, wherein the off state white structurecomprises between 5 percent and 40 percent by volume fraction of thecore-shell particles.
 5. The light emitting device of claim 2, whereineach of the plurality of core shell particles has a diameter of between1 μm and 50 μm.
 6. The light emitting device of claim 2, wherein thecore material comprises silicone in a ratio of 50% to 90% silicone tothe phase change material by weight.
 7. The light emitting device ofclaim 2, wherein the core material comprises a nucleation agent.
 8. Thelight emitting device of claim 2, wherein the phase change material hasa melting point of between 43° C. and 100° C.
 9. The light emittingdevice of claim 2, wherein the phase change material is deuterated. 10.The light emitting device of claim 2, wherein the phase change materialis selected from the group consisting of paraffin, deuterated paraffin,tricosane, deuterated tricosane, docosane, deuterated docosane,hexacosane, deuterated hexacosane, octacosane, and deuteratedoctacosane.
 11. The light emitting device of claim 2, wherein the shellis a polymer or inorganic shell.
 12. The light emitting device of claim2, wherein the shell is deuterated.
 13. The light emitting device ofclaim 2, wherein: the wavelength converting structure comprises a firstsurface adjacent the light emitting semiconductor structure and a secondsurface opposite the first surface; the off state white structure is indirect contact with the second surface of the wavelength convertingstructure; and the phase change material comprises deuterated paraffin.14. The light emitting device of claim 13, wherein the core materialcomprises silicone in a ratio of 50% to 90% silicone to the phase changematerial by weight.
 15. The light emitting device of claim 13, whereinthe core material comprises a nucleation agent.
 16. The light emittingdevice of claim 13, wherein the shell is deuterated.
 17. A lightemitting device comprising: a light emitting structure; and an off statewhite structure arranged in an optical path of light emitted by thelight emitting structure and comprising core-shell particles dispersedin a transparent material, each of the core shell particles comprising acore material that includes a phase-change material encased in a shell.18. The light emitting device of claim 17, wherein the phase changematerial has a melting point of between 43° C. and 100° C.
 19. The lightemitting device of claim 17, wherein the phase change material isdeuterated.
 20. The light emitting device of claim 17, wherein the corematerial comprises a nucleation agent.
 21. The light emitting device ofclaim 17, wherein the shell is deuterated.